Chapter II. Synthesis of α,β-unsaturated ketones through nickel-catalysed aldehyde-free
2.5. Experimental
2.5.7. Characterization Data
(E)-1-(4-Methoxyphenyl)-4,4-dimethylpent-2-en-1-one (3)54: method GP-III; a colorless oil (35 mg, 81%); 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.9 Hz, 2H), 7.04 (d, J = 15.6 Hz, 1H), 6.95 (d, J = 8.9 Hz, 2H), 6.78 (d, J = 15.6 Hz, 1H), 3.87 (s, 3H), 1.15 (s, 9H).
(E)-4,4-Dimethyl-1-phenylpent-2-en-1-one (4)54:method GP-III; a colorless oil (17 mg, 45%); 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 7.0 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.4 Hz, 2H), 7.06 (d, J = 15.7 Hz, 1H), 6.78 (d, J = 15.6 Hz, 1H), 1.16 (s, 9H).
(E)-4,4-Dimethyl-1-(p-tolyl)pent-2-en-1-one (5): method GP-III; a yellow oil (28 mg, 70%); 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 7.9 Hz, 2H), 7.26 (d, J = 7.9 Hz, 2H), 7.05 (d, J = 15.6 Hz, 1H), 6.78 (d, J = 15.6 Hz, 1H), 2.41 (s, 3H), 1.15 (s, 9H);
13C NMR (100 MHz, CDCl3)δ 191.2, 159.2, 143.4, 135.8, 129.3, 128.8, 121.0, 34.3, 28.9, 21.8; HRMS (ESI): m/z [M+H]+ calcd for (C14H19O+): 203.14304, found: 203.14302.
(E)-1-(4-Ethylphenyl)-4,4-dimethylpent-2-en-1-one (6): method GP-III; a yellow oil (27 mg, 62%);
1H NMR (400 MHz, CDCl3)δ 7.86 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.05 (d, J = 15.7 Hz, 1H), 6.78 (d, J = 15.7 Hz, 1H), 2.71 (q, J = 7.7 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.3, 159.3, 149.7, 136.0, 128.9, 128.1, 121.1, 34.3, 29.1, 28.9, 15.4; HRMS (ESI): m/z [M+H]+ calcd for (C15H21O+): 217.15869, found: 217.15868.
(E)-1-(4-Isopropylphenyl)-4,4-dimethylpent-2-en-1-one (7): method GP-III; a yellow oil (29 mg, 63%); 1H NMR (400 MHz, CDCl3)δ 7.87 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.2 Hz, 2H), 7.04 (d, J = 15.7 Hz, 1H), 6.77 (d, J = 15.7 Hz, 1H), 2.97 (m,1H), 1.28 (d, J = 6.9 Hz, 6H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.3, 159.2, 154.2, 136.2, 128.9, 126.7, 121.1, 34.4, 34.3, 28.9, 23.9; HRMS (ESI): m/z [M+H]+ calcd for (C16H23O+): 231.17434, found: 231.17424.
(E)-1-(4-(Tert-butyl)phenyl)-4,4-dimethylpent-2-en-1-one (8): method GP-III; an orange oil (30 mg, 62%); 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 8.5 Hz, 2H), 7.05 (d, J = 15.7 Hz, 1H), 6.78 (d, J = 15.7 Hz, 1H), 1.35 (s, 9H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.3, 159.2, 156.4, 135.7, 128.6, 125.6, 121.1, 35.2, 34.3, 31.3, 28.9; HRMS (ESI): m/z [M+H]+ calcd for (C17H25O+): 245.18999, found: 245.18990.
(E)-1-([1,1'-Biphenyl]-4-yl)-4,4-dimethylpent-2-en-1-one (9): method GP-IV; a white solid (21 mg, 40%); m.p. 127 ℃; 1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.4 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.64 (d, J = 7.0 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.40 (t, J = 7.3 Hz, 1H), 7.10 (d, J = 15.7 Hz, 1H), 6.83 (d, J = 15.7 Hz, 1H), 1.18 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 191.2, 159.7, 145.5, 140.2, 137.1, 129.3, 129.1, 128.3, 127.4, 127.3, 121.1, 34.4, 28.9; HRMS (ESI): m/z [M+H]+ calcd for (C19H21O+): 265.15869, found: 265.15851.
(E)-1-(4-Ethoxyphenyl)-4,4-dimethylpent-2-en-1-one (10): method GP-III; a colorless oil (37 mg, 79%); 1H NMR (400 MHz, CDCl3)δ 7.93 (d, J = 8.9 Hz, 2H), 7.03 (d, J = 15.6 Hz, 1H), 6.93 (d, J = 8.9 Hz, 2H), 6.78 (d, J = 15.6 Hz, 1H), 4.09 (q, J = 7.0 Hz, 2H), 1.44 (t, J = 7.0 Hz, 3H), 1.14 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 189.9, 162.8, 158.6, 131.0, 130.9, 120.7, 114.3, 63.8, 34.2, 28.9, 14.8; HRMS (ESI): m/z [M+H]+ calcd for (C15H21O2+): 233.15361, found: 233.15346.
(E)-1-(4-(Benzyloxy)phenyl)-4,4-dimethylpent-2-en-1-one (11): method GP-III; a white solid (38 mg, 64%); m.p. 107 ℃; 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.9 Hz, 2H), 7.46 – 7.32 (m, 5H), 7.04 (d, J = 15.6 Hz, 1H), 7.03 (d, J = 8.9 Hz, 2H), 6.78 (d, J = 15.6 Hz, 1H), 5.14 (s, 2H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 190.0, 162.5, 158.8, 136.4, 131.4, 131.0, 128.8, 128.4, 127.6, 120.7, 114.7, 70.3, 34.3, 29.0;
HRMS (ESI): m/z [M+H]+ calcd for (C20H23O2+): 295.16926, found: 295.16910.
(E)-4,4-Dimethyl-1-(4-phenoxyphenyl)pent-2-en-1-one (12): method GP-IV; an orange solid (32 mg, 57%); m.p. 117 ℃; 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.8 Hz, 2H), 7.43 – 7.36 (m, 2H), 7.19 (t, J = 7.4 Hz, 1H), 7.09 – 7.00 (m, 4H), 7.05 (d, J = 15.6 Hz, 1H), 6.77 (d, J = 15.6 Hz, 1H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 190.1, 161.8, 159.3, 155.8, 132.9, 130.9, 130.2, 124.7, 120.8, 120.2, 117.5, 34.3, 28.9; HRMS (ESI): m/z [M+H]+ calcd for (C19H21O2+): 281.15361, found: 281.15341.
(E)-1-(4-Hydroxyphenyl)-4,4-dimethylpent-2-en-1-one (13): method GP-III; an orange oil (20 mg, 48%); 1H NMR (400 MHz, CDCl3)δ 7.90 (d, J = 8.7 Hz, 2H), 7.09 (br, 1H), 7.06 (d, J = 15.6 Hz, 1H), 6.93 (d, J = 8.8 Hz, 2H), 6.79 (d, J = 15.6 Hz, 1H), 1.14 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 190.9, 160.8, 159.5, 131.4, 130.7, 120.7, 115.6, 34.3, 28.9; HRMS (ESI): m/z [M+H]+ calcd for (C13H17O2+): 205.12231, found:
205.12222.
(E)-1-(4-Fluorophenyl)-4,4-dimethylpent-2-en-1-one (14)54:method GP-III; a white solid (10 mg, 25%); 1H NMR (400 MHz, CDCl3) δ 7.96 (dd, J = 8.8, 5.5 Hz, 2H), 7.14 (t, J = 8.6 Hz, 2H), 7.06 (d, J = 15.7 Hz, 1H), 6.75 (d, J = 15.6 Hz, 1H), 1.16 (s, 9H).
(E)-1-(4-Chlorophenyl)-4,4-dimethylpent-2-en-1-one (15)54: method GP-IV; a white solid (19 mg, 43%); 1H NMR (400 MHz, CDCl3) δ 7.87 (d, J = 8.6 Hz, 2H), 7.44 (d, J = 8.6 Hz, 2H), 7.07 (d, J = 15.6 Hz, 1H), 6.73 (d, J = 15.6 Hz, 1H), 1.15 (s, 9H).
(E)-1-(4-Bromophenyl)-4,4-dimethylpent-2-en-1-one (16)54:method GP-III; a colorless oil (16 mg, 30%); 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J = 8.6 Hz, 2H), 7.61 (d, J = 8.6 Hz, 2H), 7.06 (d, J = 15.7 Hz, 1H), 6.72 (d, J = 15.7 Hz, 1H), 1.15 (s, 9H).
Methyl (E)-4-(4,4-dimethylpent-2-enoyl)benzoate (17): method GP-IV; a white solid (10 mg, 21%);
m.p. 95 ℃; 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 8.6 Hz, 2H), 7.95 (d, J = 8.6 Hz, 2H), 7.07 (d, J = 15.7 Hz, 1H), 6.75 (d, J = 15.7 Hz, 1H), 3.95 (s, 3H), 1.16 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.3, 166.5, 161.0, 141.9, 129.9, 129.7, 128.5, 121.1, 52.6, 34.5, 28.8; HRMS (ESI): m/z [M+H]+ calcd for (C15H19O3+):
247.13287, found: 247.13271.
(E)-4,4-Dimethyl-1-(4-(trifluoromethyl)phenyl)pent-2-en-1-one (18)55: method GP-IV; a white solid (12 mg, 23%); 1H NMR (400 MHz, CDCl3)δ 8.00 (d, J = 8.1 Hz, 2H), 7.73 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 15.7 Hz, 1H), 6.74 (d, J = 15.8 Hz, 1H), 1.16 (s, 9H).
(E)-4,4-Dimethyl-1-(m-tolyl)pent-2-en-1-one (19): method GP-III; a yellow oil (22 mg, 54%); 1H NMR (400 MHz, CDCl3) δ 7.72 (m, 2H), 7.36 (m, 2H), 7.05 (d, J = 15.7 Hz, 1H), 6.77 (d, J = 15.7 Hz, 1H), 2.42 (s, 3H), 1.16 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.9, 159.6, 138.4, 138.4, 133.5, 129.2, 128.5, 125.9, 121.2, 34.3, 28.9, 21.5; HRMS (ESI): m/z [M+H]+ calcd for (C14H19O+): 203.14304, found: 203.14308.
(E)-1-(3-Methoxyphenyl)-4,4-dimethylpent-2-en-1-one (20): method GP-IV; a colorless oil (18 mg, 42%); 1H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 7.7 Hz, 1H), 7.45 (s, 1H), 7.37 (t, J = 7.9 Hz, 1H), 7.10 (ddd, J = 8.2, 2.7, 0.9 Hz, 1H), 7.05 (d, J = 15.7 Hz, 1H), 6.75 (d, J = 15.7 Hz, 1H), 3.86 (s, 3H), 1.15 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 191.5, 159.9, 159.8, 139.8, 129.6, 121.2, 121.1, 119.1, 113.1, 55.6, 34.3, 28.9; HRMS
(ESI): m/z [M+H]+ calcd for (C14H19O2+): 219.13796, found: 219.13788.
(E)-1-(3-Ethoxyphenyl)-4,4-dimethylpent-2-en-1-one (21): method GP-IV; a colorless oil (21 mg, 45%); 1H NMR (400 MHz, CDCl3)δ 7.48 (d, J = 7.6 Hz, 1H), 7.44 (s, 1H), 7.36 (t, J = 7.9 Hz, 1H), 7.11 – 7.07 (m, 1H), 7.05 (d, J = 15.7 Hz, 1H), 6.75 (d, J = 15.7 Hz, 1H), 4.09 (q, J = 6.9 Hz, 2H), 1.43 (t, J = 7.0 Hz, 3H), 1.15 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 191.5, 159.7, 159.2, 139.7, 129.6, 121.1, 121.1, 119.5, 113.8, 63.8, 34.3, 28.9, 14.9; HRMS (ESI): m/z [M+H]+ calcd for (C15H21O2+): 233.15361, found: 233.15364.
(E)-1-(2-Methoxyphenyl)-4,4-dimethylpent-2-en-1-one (22): method GP-IV; a colorless oil (26 mg, 58%); 1H NMR (400 MHz, CDCl3) δ 7.50 (dd, J = 7.6, 1.8 Hz, 1H), 7.47 – 7.40 (m, 1H), 7.00 (t, J = 7.5 Hz, 1H), 6.96 (d, J = 8.3 Hz, 1H), 6.83 (d, J = 15.8 Hz, 1H), 6.58 (d, J = 15.8 Hz, 1H), 3.86 (s, 3H), 1.11 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 194.3, 158.4, 157.8, 132.5, 130.2, 129.4, 125.9, 120.6, 111.6, 55.6, 33.9, 28.8; HRMS (ESI):
m/z [M+H]+ calcd for (C14H19O2+): 219.13796, found: 219.13792.
(E)-1-(2-Ethoxyphenyl)-4,4-dimethylpent-2-en-1-one (23):method GP-IV; a yellow oil (29 mg, 62%); 1H NMR (400 MHz, CDCl3)δ 7.56 (dd, J = 7.6, 1.8 Hz, 1H), 7.43 – 7.37 (m, 1H), 6.98 (t, J = 7.5 Hz, 1H), 6.92 (d, J = 8.3 Hz, 1H), 6.88 (d, J = 15.8 Hz, 1H), 6.73 (d, J = 15.8 Hz, 1H), 4.08 (q, J = 7.0 Hz, 2H), 1.42 (t, J = 7.0 Hz, 3H), 1.11 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 194.0, 157.6, 157.4, 132.8, 130.5, 129.6, 126.1, 120.7, 112.5, 64.2, 34.0, 28.9, 15.0; HRMS (ESI): m/z [M+H]+ calcd for (C15H21O2+): 233.15361, found: 233.15349.
(E)-4,4-Dimethyl-1-(o-tolyl)pent-2-en-1-one (24): method GP-III; a yellow oil (26 mg, 64%); 1H NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.5 Hz, 1H), 7.34 (d, J = 7.4 Hz, 1H), 7.25 – 7.21 (m, 2H), 6.71 (d, J = 16.0 Hz, 1H), 6.40 (d, J = 16.0 Hz, 1H), 2.39 (s, 3H), 1.11 (s, 9H); 13C NMR (100 MHz, CDCl3)δ 197.8, 161.1, 139.4, 136.8, 131.3, 130.3, 128.2, 126.0, 125.5, 34.2, 28.8, 20.3; HRMS (ESI): m/z [M+H]+ calcd for (C14H19O+): 203.14304, found: 203.14302.
(E)-4,4-Dimethyl-1-(naphthalen-2-yl)pent-2-en-1-one (25)54: method GP-III; an orange oil (21 mg, 44%); 1H NMR (400 MHz, CDCl3)δ 8.44 (s, 1H), 8.02 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 8.3 Hz, 1H), δ 7.91 (d, J = 9.0 Hz, 1H), δ 7.89 (d, J = 8.0 Hz, 1H), 7.62 – 7.53 (m, 2H), 7.14 (d, J = 15.7 Hz, 1H), 6.94 (d, J = 15.7 Hz, 1H), 1.20 (s, 9H).
(E)-4,4-Dimethyl-1-(naphthalen-1-yl)pent-2-en-1-one (26)55:method GP-III; a white solid (15 mg, 32%); 1H NMR (400 MHz, CDCl3)δ 8.26 (d, J = 7.4 Hz, 1H), 7.97 (d, J = 8.3 Hz, 1H), 7.89 (d, J = 7.0 Hz, 1H), 7.66 (d, J = 7.1 Hz, 1H), 7.56 – 7.50 (m, 3H), 6.86 (d, J = 16.0 Hz, 1H), 6.58 (d, J = 16.0 Hz, 1H), 1.12 (s, 9H).
(E)-4,4-Dimethyl-1-(1-methyl-1H-indol-3-yl)pent-2-en-1-one (27): method GP-IV; a yellow solid (39 mg, 82%); m.p. 135 ℃; 1H NMR (400 MHz, CDCl3)δ 8.48 – 8.43 (m, 1H), 7.76 (s, 1H), 7.36 – 7.30 (m, 3H), 7.05 (d, J = 15.5 Hz, 1H), 6.65 (d, J = 15.5 Hz, 1H), 3.86 (s, 3H), 1.17 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 185.6, 155.5, 137.7, 135.4, 127.0, 123.6, 123.1, 122.7, 122.3, 117.5, 109.7, 33.9, 33.7, 29.1;
HRMS (ESI): m/z [M+H]+ calcd for (C16H20NO+): 242.15394, found: 242.15375.
(E)-2,2,6,6-Tetramethylhept-4-en-3-one (28)55:method GP-III; a yellow oil (14 mg, 43%); 1H NMR (400 MHz, CDCl3)δ 6.93 (d, J = 15.4 Hz, 1H), 6.39 (d, J = 15.5 Hz, 1H), 1.15 (s, 9H), 1.08 (s, 9H).
(E)-2,2-Dimethylnon-3-en-5-one (29)56:method GP-III; a yellow oil (10 mg, 30%); 1H NMR (400 MHz, CDCl3) δ 6.81 (d, J = 16.1 Hz, 1H), 6.01 (d, J = 16.1 Hz, 1H), δ 2.54 (t, J = 7.7 Hz, 2H), 1.61 – 1.56 (m, 2H), 1.37 – 1.32 (m, 2H), 1.08 (s, 9H), 0.92 (t, J = 7.3 Hz, 3H).
(E)-1-Cyclopropyl-4,4-dimethylpent-2-en-1-one (30): method GP-III; a yellow oil (17 mg, 56%); 1H NMR (400 MHz, CDCl3)δ 6.89 (d, J = 16.1 Hz, 1H), 6.15 (d, J = 16.1 Hz, 1H), 2.15 (tt, J = 7.9, 4.6 Hz, 1H), 1.11 (s, 9H), 1.08 (dt, J = 4.3, 3.1 Hz, 2H), 0.91 (dt, J = 8.1, 3.4 Hz, 2H); 13C NMR (100 MHz, CDCl3)δ 201.1, 156.7, 125.8, 33.9, 28.9, 19.0,
11.3; HRMS (ESI): m/z [M+H]+ calcd for (C10H17O+): 153.12739, found: 153.12737.
(E)-1-Cyclopentyl-4,4-dimethylpent-2-en-1-one (31): method GP-III; an orange oil (14 mg, 40%);
1H NMR (400 MHz, CDCl3) δ 6.84 (d, J = 16.0 Hz, 1H), 6.05 (d, J = 16.0 Hz, 1H), 3.10 (m, 1H), 1.85 – 1.71 (m, 4H), 1.64 – 1.54 (m, 4H), 1.08 (d, J = 1.3 Hz, 9H); 13C NMR (100 MHz, CDCl3)δ 203.5, 157.0, 124.7, 49.2, 33.9, 29.5, 28.9, 26.3; HRMS (ESI): m/z [M+H]+ calcd for (C12H21O+): 181.15869, found: 181.15865.
(E)-1-Cyclohexyl-4,4-dimethylpent-2-en-1-one (32)31:method GP-IV; a yellow oil (28 mg, 73%); 1H NMR (400 MHz, CDCl3)δ 6.84 (d, J = 16.0 Hz, 1H), 6.06 (d, J = 16.0 Hz, 1H), 2.56 (m, 1H), 1.71 – 1.62 (m, 2H), 1.42 – 1.16 (m, 8H), 1.08 (d, J = 1.3 Hz, 9H).
(E)-1-(4-Methoxyphenyl)-2-buten-1-one (33)57:method GP-IV; a colorless oil (24 mg, 68%); 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.9 Hz, 2H), 7.05 (dq, J = 15.3, 6.8 Hz, 1H), 6.96 – 6.89 (m, 3H), 3.87 (s, 3H), 1.99 (dd, J = 6.7, 1.5 Hz, 3H).
(E)-1-(4-Methoxyphenyl)-4-methylpent-2-en-1-one (34)58: method GP-IV; a yellow oil (20 mg, 48%); 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.8 Hz, 2H), 7.01 (dd, J = 15.4, 6.7 Hz, 1H), 6.94 (d, J = 8.8 Hz, 2H), 6.83 (dd, J = 15.4, 1.3 Hz, 1H), 3.87 (s, 3H), 2.56 (m, 1H), 1.13 (d, J = 6.8 Hz, 6H).
(E)-3-Cyclopropyl-1-(4-methoxyphenyl)prop-2-en-1-one (35): method GP-IV; a yellow oil (10 mg, 25%); 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.4 Hz, 2H), 7.03 (d, J = 15.0 Hz, 1H), 6.94 (d, J = 8.4 Hz, 2H), 6.54 (dd, J = 15.0, 10.2 Hz, 1H), 3.87 (s, 3H), 1.73 – 1.65 (m, 1H), 1.04 – 0.97 (m, 2H), 0.72 (m, 2H); 13C NMR (100 MHz, CDCl3)δ 188.3, 163.3, 154.3, 131.1, 130.8, 122.6, 113.8, 55.6, 15.4, 9.2; HRMS (ESI): m/z [M+H]+ calcd for (C13H15O2+): 203.10666, found: 203.10660.
(E)-3-Cyclopentyl-1-(4-methoxyphenyl)prop-2-en-1-one (36): method GP-IV; a brown oil (15 mg, 33%); 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.9 Hz, 2H), 7.03 (dd, J = 15.3, 8.0 Hz, 1H), 6.94 (d, J = 8.9 Hz, 2H), 6.86 (dd, J = 15.3, 0.9 Hz, 1H), 3.87 (s, 3H), 2.70 (m, 1H), 1.95 – 1.83 (m, 2H), 1.78 – 1.67 (m, 2H), 1.69 – 1.57 (m, 2H), 1.55 – 1.40 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 189.5, 163.4, 153.4, 131.1, 130.9, 123.7, 113.8, 55.6, 43.6, 32.8, 25.5; HRMS (ESI): m/z [M+H]+ calcd for (C15H19O2+): 231.13796, found: 231.13791.
(E)-3-Cyclohexyl-1-(4-methoxyphenyl)prop-2-en-1-one (37): method GP-IV; a yellow solid (30 mg, 62%); m.p. 64 ℃; 1H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 8.9 Hz, 2H), 6.99 (dd, J = 15.5, 6.8 Hz, 1H), 6.94 (d, J = 8.9 Hz, 2H), 6.83 (dd, J = 15.5, 1.3 Hz, 1H), 3.87 (s, 3H), 2.24 (m, 1H), 1.87 – 1.75 (m, 4H), 1.37 – 1.19 (m, 6H); 13C NMR (100 MHz, CDCl3)δ 189.7, 163.4, 154.0, 131.2, 130.9, 123.2, 113.8, 55.6, 41.2, 32.1, 26.1, 25.9; HRMS (ESI): m/z [M+H]+ calcd for (C16H21O2+): 245.15361, found: 245.15356.
(E)-1-(4-Methoxyphenyl)-4-phenylbut-2-en-1-one (38): method GP-IV; a yellow oil (29 mg, 57%);
1H NMR (400 MHz, CDCl3) δ 7.91 (d, J = 8.9 Hz, 2H), 7.38 – 7.29 (m, 2H), 7.26 – 7.21 (m, 3H), 7.20 – 7.14 (m, 1H), 6.93 (d, J = 8.9 Hz, 2H), 6.87 (dt, J = 15.3, 1.6 Hz, 1H), 3.87 (s, 3H), 3.64 (d, J = 6.8 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 189.1, 163.5, 146.8, 131.0, 130.8, 129.0, 128.9, 126.8, 126.6, 113.9, 100.1, 55.6, 39.1; HRMS (ESI): m/z [M+H]+ calcd for (C17H17O2+): 253.12231, found: 253.12215.
(E)-1-(4-Methoxyphenyl)-3-phenylprop-2-en-1-one (39)59: method GP-IV; a yellow solid (32 mg, 67%); 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.8 Hz, 2H), 7.81 (d, J = 15.7 Hz, 1H), 7.68 – 7.62 (m, 2H), 7.55 (d, J = 15.7 Hz, 1H), 7.45 – 7.39 (m, 3H), 6.99 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H).
(E)-1-(4-Methoxyphenyl)-3-(p-tolyl)prop-2-en-1-one (40)60:method GP-IV; a white solid (35 mg, 69%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.79 (d, J = 15.6 Hz, 1H), 7.58 – 7.45 (m, 3H), 7.22 (d, J = 7.9 Hz, 2H), 6.98 (d, J = 8.9 Hz, 2H), 3.89 (s, 3H), 2.39 (s, 3H).
(E)-3-(4-Ethylphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (41)59: method GP-IV; a yellow solid (32 mg, 60%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.80 (d, J = 15.6 Hz, 1H), 7.57 (d, J = 8.1 Hz, 2H), 7.51 (d, J = 15.6 Hz, 1H), 7.25 (d, J = 7.5 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H), 2.69 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H).
(E)-3-(4-(Tert-butyl)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (42)60: method GP-IV; a yellow solid (41 mg, 69%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.80 (d, J = 15.6 Hz, 1H), 7.59 (d, J = 8.2 Hz, 2H), 7.51 (d, J = 15.6 Hz, 1H), 7.44 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H), 1.35 (s, 9H).
(E)-1-(4-Methoxyphenyl)-3-(4-pentylphenyl)prop-2-en-1-one (43): method GP-IV; a yellow solid (35 mg, 56%); m.p. 76 ℃; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.79 (d, J = 15.6 Hz, 1H), 7.56 (d, J = 8.1 Hz, 2H), 7.51 (d, J = 15.6 Hz, 1H), 7.23 (d, J = 8.1 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 3.89 (s, 3H), 2.64 (t, J = 7.6 Hz, 2H), 1.68 – 1.61 (m, 2H), 1.37 – 1.29 (m, 4H), 0.90 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 189.0, 163.5, 146.0, 144.3, 132.7, 131.4, 130.9, 129.2, 128.6, 121.1, 114.0, 55.6, 36.0, 31.6, 31.1, 22.7, 14.2; HRMS (ESI): m/z [M+H]+ calcd for (C21H25O2+): 309.18491, found: 309.18497.
(E)-3-([1,1'-Biphenyl]-4-yl)-1-(4-methoxyphenyl)prop-2-en-1-one (44)61:method GP-IV; a yellow solid (32 mg, 50%); 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.9 Hz, 2H), 7.85 (d, J = 15.6 Hz, 1H), 7.73 (d, J = 8.2 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 6.9 Hz, 2H), 7.59 (d, J = 15.6 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H), 7.38 (t, J = 7.3 Hz, 1H), 7.00 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
(E)-1-(4-Methoxyphenyl)-3-(4-phenoxyphenyl)prop-2-en-1-one (45): method GP-IV; a white solid (43 mg, 65%); m.p. 118 ℃; 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.79 (d, J = 15.6 Hz, 1H), 7.62 (d, J = 8.7 Hz, 2H), 7.46 (d, J = 15.6 Hz, 1H), 7.38 (dd, J = 8.6, 7.4 Hz, 2H), 7.17 (t, J = 7.4 Hz, 1H), 7.07 (d, J = 7.6 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 3.89 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 188.8, 163.5, 159.7, 156.3, 143.5, 131.4, 130.9, 130.2, 130.1, 130.0, 124.3, 120.8, 119.8, 118.6, 114.0, 55.7; HRMS (ESI): m/z [M+H]+ calcd for (C22H19O3+): 331.13287, found:
331.13263.
(E)-3-(2-Methoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (46)62:method GP-IV; a yellow oil (41 mg, 76%); 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 15.8 Hz, 1H), 8.04 (d, J = 8.8 Hz, 2H), 7.64 (dd, J = 7.7, 1.6 Hz, 1H), 7.63 (d, J = 15.8 Hz, 1H), 7.40 – 7.34 (m, 1H), 7.03 – 6.92 (m, 4H), 3.92 (s, 3H), 3.89 (s, 3H).
(E)-3-(3-Methoxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (47)62: method GP-IV; a yellow solid (35 mg, 65%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.9 Hz, 2H), 7.76 (d, J = 15.6 Hz, 1H), 7.52 (d, J = 15.7 Hz, 1H), 7.34 (t, J = 7.9 Hz, 1H), 7.23 (d, J = 1.2 Hz, 1H), 7.16 (m, 1H), 7.03 – 6.92 (m, 3H), 3.90 (s, 3H), 3.86 (s, 3H).
(E)-1,3-Bis(4-methoxyphenyl)prop-2-en-1-one (48)62:method GP-IV; a yellow solid (29 mg, 54%);
1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.8 Hz, 2H), 7.78 (d, J = 15.6 Hz, 1H), 7.60 (d, J = 8.8 Hz, 2H), 7.43 (d, J = 15.5 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 6.94 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H), 3.86 (s, 3H).
(E)-3-(4-Methoxy-2-methylphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (49): method GP-IV; a yellow solid (31 mg, 55%); m.p. 128 ℃; 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 15.4 Hz, 1H), 8.04 (d, J = 8.7 Hz, 2H), 7.68 (d, J = 8.5 Hz, 1H), 7.39 (d, J = 15.4 Hz, 1H), 6.98 (d, J = 8.9 Hz, 2H), 6.83 – 6.73 (m, 2H), 3.89 (s, 3H), 3.84 (s, 3H), 2.48 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 188.9, 163.4, 161.3, 141.4, 140.7, 131.5, 130.9, 128.1, 126.9, 120.6, 116.0, 113.9, 112.3, 55.6, 55.5, 20.4; HRMS (ESI):
m/z [M+H]+ calcd for (C18H19O3+): 283.13287, found: 283.13281.
(E)-3-(4-Fluorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (50)61:method GP-IV; a white solid (35 mg, 69%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.8 Hz, 2H), 7.77 (d, J = 15.6 Hz, 1H), 7.64 (dd, J = 8.7, 5.4 Hz, 2H), 7.47 (d, J = 15.7
Hz, 1H), 7.11 (t, J = 8.6 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
(E)-3-(4-Chlorophenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (51)61:method GP-IV; a yellow solid (31 mg, 56%); 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.8 Hz, 2H), 7.75 (d, J = 15.7 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 15.6 Hz, 1H), 7.39 (d, J = 8.5 Hz, 2H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
(E)-1-(4-Methoxyphenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one (52)62:method GP-III; a yellow solid (24 mg, 39%); 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 8.9 Hz, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.74 (d, J = 8.4 Hz, 2H), 7.67 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 15.7 Hz, 1H), 7.00 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
(E)-3-(3,5-Bis(trifluoromethyl)phenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (53)63: method GP- IV; a brown oil (19 mg, 25%); 1H NMR (400 MHz, CDCl3) δ 8.07 (d, J
= 8.9 Hz, 2H), 8.04 (s, 2H), 7.89 (s, 1H), 7.81 (d, J = 15.7 Hz, 1H), 7.65 (d, J = 15.7 Hz, 1H), 7.01 (d, J = 8.9 Hz, 2H), 3.91 (s, 3H).
(E)-3-(6-Methoxynaphthalen-2-yl)-1-(4-methoxyphenyl)prop-2-en-1-one (54): method GP-IV; a yellow solid (48 mg, 76%); m.p. 167 ℃; 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 8.9 Hz, 2H), 7.95 (d, J = 15.4 Hz, 2H), 7.80 – 7.73 (m, 3H), 7.62 (d, J = 15.6 Hz, 1H), 7.21 – 7.13 (m, 2H), 7.00 (d, J = 8.9 Hz, 2H), 3.95 (s, 3H), 3.91 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 188.9, 163.5, 159.0, 144.5, 135.9, 131.5, 130.9, 130.6, 130.4, 130.3, 128.9, 127.6, 124.6, 121.1, 119.6, 114.0, 106.2, 55.7, 55.6; HRMS (ESI): m/z [M+H]+ calcd for (C21H19O3+): 319.13287, found: 319.13293.
(E)-1-(4-Methoxyphenyl)-3-(thiophen-2-yl)prop-2-en-1-one (55)61:method GP-IV; a brown solid (19 mg, 39%); 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.9 Hz, 2H), 7.93 (d, J = 15.3 Hz, 1H), 7.40 (d, J = 5.1 Hz, 1H), δ 7.35 (d, J = 3.6 Hz, 1H), δ 7.35 (d, J = 15.3 Hz, 1H), 7.09 (dd, J = 5.1, 3.6 Hz, 1H), 6.98 (d, J = 8.9 Hz, 2H), 3.89 (s, 3H).
(E)-1-(4-Methoxyphenyl)-3-(thiophen-3-yl)prop-2-en-1-one (56)64:method GP-IV; an orange oil (28 mg, 58%); 1H NMR (400 MHz, CDCl3) δ 8.02 (d, J = 8.9 Hz, 2H), 7.79 (d, J = 15.5 Hz, 1H), 7.59 (dd, J = 3.0, 1.3 Hz, 1H), 7.42 (dd, J = 5.1, 1.3 Hz, 1H), δ 7.38 – 7.36 (m, 1H), δ 7.36 (d, J = 15.6 Hz, 1H), 6.98 (d, J = 8.9 Hz, 2H), 3.89 (s, 3H).
(E)-3-(3-Hydroxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one (57)65: method GP-IV; a yellow solid (32 mg, 62%); 1H NMR (400 MHz, DMSO-d6) δ 9.62 (s, 1H), 8.16 (d, J = 8.9 Hz, 2H), 7.84 (d, J = 15.6 Hz, 1H), 7.61 (d, J = 15.5 Hz, 1H), 7.31 (d, J = 7.7 Hz, 1H), 7.25 (t, J = 7.7 Hz, 1H), 7.22 (t, J = 2.0 Hz, 1H), 7.09 (d, J = 9.0 Hz, 2H), 6.87 (d, J = 7.8 Hz, 1H), 3.87 (s, 3H).
(8R,9S,10R,13S,14S,17R)-17-Hydroxy-17-((E)-3-(4-methoxyphenyl)-3-oxoprop-1-en-1-yl)-10,13- dimethyl-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one (58): method 1 mmol scale; a white solid (263 mg, 59%); m.p. 116 ℃; 1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.9 Hz, 2H), δ 7.23 (d, J = 15.2 Hz, 1H), 7.17 (d, J = 15.1 Hz, 1H), 6.95 (d, J = 8.9 Hz, 2H), 5.73 (s, 1H), 3.88 (s, 3H), 2.44 – 2.27 (m, 4H), 2.05 – 1.95 (m, 2H), 1.94 – 1.82 (m, 2H), 1.71 – 1.36 (m, 10H), 1.19 (s, 3H), 1.12 – 1.06 (m, 1H), 1.01 (s, 3H), 0.97 – 0.92 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 199.6, 188.7, 170.9, 163.7, 151.8, 131.1, 124.2, 121.7, 114.0, 84.6, 55.6, 53.5, 50.4, 47.7, 38.7, 37.7, 36.5, 35.8, 34.1, 32.9, 32.7, 31.7, 29.9, 24.0, 20.8, 17.6, 14.0; HRMS (ESI): m/z [M+H]+ calcd for (C29H37O4+): 449.26864, found: 449.26852.
(E)-1-(4-Methoxyphenyl)-2-methyl-3-phenylprop-2-en-1-one (59)66:method GP-III; a colorless oil (15 mg, 30%); 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.8 Hz, 2H), 7.44 – 7.39 (m, 4H), 7.36 – 7.31 (m, 1H), 7.11 (d, J = 1.5 Hz, 1H), 6.95 (d, J = 8.8 Hz, 2H), 3.88 (s, 3H), 2.26 (d, J = 1.5 Hz, 3H).
(E)-1-(4-Methoxyphenyl)-2,3-diphenylprop-2-en-1-one (60)67:method GP-III; a colorless oil (8 mg, 13%); 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.9 Hz, 2H), 7.34 – 7.28 (m, 5H), 7.22 – 7.16 (m, 3H), 7.14 (s, 1H), 7.11 (d, J = 7.5 Hz, 2H), 6.92 (d, J = 8.8
Hz, 2H), 3.87 (s, 3H).
(E)-1-(4-Methoxyphenyl)-2-propylhex-2-en-1-one (61)66:method GP-III; a colorless oil (5 mg, 10%);
1H NMR (400 MHz, CDCl3) δ 7.71 (d, J = 8.8 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 6.10 (t, J = 7.3 Hz, 1H), 3.86 (s, 3H), 2.50 – 2.39 (m, 2H), 2.26 (m, 2H), 1.46 (m, 4H), 1.00 – 0.90 (m, 6H).
Methyl 4-(4-methoxyphenyl)-4-oxobutanoate (62)68:method GP-III; a white solid (29 mg, 66%); 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.9 Hz, 2H), 6.92 (d, J = 8.9 Hz, 2H), 3.86 (s, 3H), 3.69 (s, 3H), 3.26 (t, J = 6.7 Hz, 2H), 2.74 (t, J = 6.7 Hz, 2H).
Ethyl 4-(4-methoxyphenyl)-4-oxobutanoate (63)69:method GP-III; a white solid (31 mg, 65%); 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.9 Hz, 2H), 6.93 (d, J = 8.9 Hz, 2H), 4.15 (q, J = 7.1 Hz, 2H), 3.86 (s, 3H), 3.26 (t, J = 6.7 Hz, 2H), 2.73 (t, J = 6.7 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H).
4-(4-Methoxyphenyl)-4-oxobutanenitrile (64)33:method GP-III; a white solid (28 mg, 74%); 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 9.0 Hz, 2H), 6.95 (d, J = 9.0 Hz, 2H), 3.87 (s, 3H), 3.36 – 3.27 (t, J = 7.2 Hz, 2H), 2.79 – 2.70 (t, J = 7.2 Hz, 2H).
2,2,6,6-Tetramethylpiperidin-1-yl 4-methoxybenzoate (65)33: a colorless oil (41 mg, 70%); 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 9.0 Hz, 2H), 6.94 (d, J = 9.0 Hz, 2H), 3.87 (s, 3H), 1.82 – 1.58 (m, 5H), 1.49 – 1.41 (m, 1H), 1.26 (s, 6H), 1.11 (s, 6H).
(2Z,4E)-1-(4-Methoxyphenyl)-2,3,4,5-tetraphenylpenta-2,4-dien-1-one (66): a yellow solid (16 mg, 16%); m.p. 70 ℃; 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 7.2 Hz, 2H), 7.47 (d, J = 6.2 Hz, 2H), 7.33 – 7.30 (m, 2H), 7.25 – 7.07 (m, 16H), 6.91 (s, 1H), 6.35 (d, J = 9.0 Hz, 2H), 3.68 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 195.5, 162.2, 143.0, 141.8, 140.9, 140.7, 138.0, 137.9, 137.8, 132.0, 131.2, 130.6, 129.5, 128.8, 128.8, 128.4, 128.2, 128.2, 128.1, 128.0, 127.9, 127.7, 127.7, 127.3, 113.0, 55.3; HRMS
(ESI): m/z [M+H]+ calcd for (C36H29O2+): 493.21621, found: 493.21655.
1-(4-Methoxyphenyl)-2,3,4,5-tetraphenylcyclopenta-2,4-dien-1-ol (67): a white solid (39 mg, 40%), m.p. 200 ℃; 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.8 Hz, 2H), 7.19 – 6.93 (m, 20H), 6.80 (d, J = 8.9 Hz, 2H), 3.77 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.6, 148.0, 142.3, 135.2 134.1, 132.1, 130.1, 129.7, 128.0, 127.9, 127.2, 127.1, 126.4, 114.0, 90.1, 55.3; HRMS (ESI): m/z [M+H]+ calcd for (C36H29O2+):
493.21621, found: 493.21616.